Graduation Year


Document Type




Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Civil and Environmental Engineering

Major Professor

A. Zayed, Ph.D.

Committee Member

Gray Mullins, Ph.D.

Committee Member

Aydin Sunol, Ph.D.

Committee Member

Mahmood Nachabe, Ph.D.

Committee Member

Kyle Riding, Ph.D.


accelerator, heat of hydration, autogenous shrinkage, rheology, microstructure


The use of supplementary cementitious materials (SCMs) in commercial construction have been increasing over the last several decades as climate change and sustainability has been gaining global attention. Incorporation of SCMs into concrete mixtures provides several environmental benefits. Since most SCMs are waste by-products of other industries, their use in concrete reduces waste disposal. Additionally, cements substitution with SCMs reduces the carbon footprint of the construction industry. Cement production generates large amounts of CO2 emissions; the use of SCMs reduces the amount of cement in a concrete mixture thereby reducing emissions from its production.

In addition to SCMs, modern concretes typically incorporate a combination of chemical admixtures. Adverse interaction of admixtures with cement, with or without the SCMs, or with each other is one of the most common reasons for early-age concrete issues. Since the possible combinations of admixtures are numerous and there is a variety of cements on the market, testing all possible chemical/mineral/cement admixture combinations is impractical.

The aim of this research was to cover a broad base of admixture-related issues, each addressing a specific need of the construction industry. There is currently no explanation for why calcium chloride-based accelerator is not always effective when used with high tricalcium aluminate (C3A) cements. It was determined that increasing C3A or gypsum content alone did not appear to significantly affect acceleration; however, the presence of alkalis reduced the effectiveness of CaCl2 accelerator.

When CaCl2-based accelerators are used in concrete, they are typically used in combination with other chemical admixtures, such as water-reducing and retarding admixtures (WRRA) to allow for the use of a low water-cementitious material ratio. In order to avoid premature hardening, CaCl2 accelerator is most often added onsite, rather than at the concrete batching plant. Onsite addition can lead to accidental overdose of accelerator. It was found that increasing dosages of calcium chloride-containing accelerating admixtures in the presence of WRRA has a non-linear effect on the pore size distribution and consequently a non-linear increase on the autogenous shrinkage, which can contribute to early-age concrete cracking.

Water-reducing admixtures and superplasticizers are added to concrete to improve workability, which decreases not only with a decrease in water-cementitious material ratio, but also with addition of some SCMs. Silica fume and metakaolin are known to decrease workability; fly ash and slag addition improve it. The effect of SCM combinations on workability is typically assumed to be additive. However, this investigation revealed that combining SCMs does not have an additive effect on workability, measured in terms of apparent yield stress and plastic viscosity; consequently, these parameters cannot be estimated from their respective values.

Cement replacement with SCMs affects not only workability, but also heat of hydration, and is commonly used to reduce concrete temperature rise in concrete. Prediction and control of concrete temperature rise due to cement hydration is of great significance for mass concrete structures since large temperature gradients between the surface and the core of the structure can lead to cracking thus reducing durability of the structure. A number of equations have been proposed to predict the heat of hydration of cement and cement/SCM blends. However, these equations do not include metakaolin, which is a relatively new mineral admixture. Based on statistical experimental design, an equation was developed to predict the reduction of total hydration heat at 24, 48 and 72 hours with addition of SCMs compared to a plain ordinary portland cement (OPC)-water mixture. The developed equation allows the evaluation of the contribution of Class F fly ash (FA), blast furnace slag (BFS), silica fume (SF) and metakaolin (MK) as well as their combinations.

Since metakaolin has been on the market for only about 10 years, the current knowledge on its effect on hydration products and paste microstructure remains incomplete. The effect of MK on the nature of hydration products was evaluated through x-ray diffraction. Its effect on the microstructure was assessed by measuring porosity with nitrogen adsorption and determining nanoindentation modulus as well as the volume fraction of calcium silicate hydrates (C-S-H) with variable packing densities. No significant effect was observed on the nature of hydration products with MK or BFS addition. However, nitrogen-accessible porosity increased with MK and BFS addition, the increase being larger with BFS. The average indentation modulus for the hydration products decreased with addition of MK and BFS, which corresponded to increasing nitrogen accessible pores. The results of this study indicate that phase quantification by quantitative x-ray diffraction (QXRD) of the hydrated paste may not be sufficient to assess the impact of metakaolin or BFS addition on the hydrating cementitious systems, and a multi-technique approach that provides information not only on the amount of hydration products, but also their morphology is preferable.